Norbornyl dimer ester and polyester additives for lubricants and fuels

ABSTRACT

Novel dimer esters and polyesters derived from and adduct of 5-norbornene-2,3-dicarboxylic anhydride and O,O-dialkyldithiophosphoric acid have been produced. These dimer esters and polyesters are useful extreme pressure agents, antiwear agents and oxidation inhibitors as well as friction modifying agents for functional fluids used in motorized vehicles.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel norbornyl dimer ester and polyesteradditives for functional fluids. It has been discovered that theseadditives improve the extreme pressure, antiwear, antioxidant andfriction modifying properties of functional fluids, e.g., lubricants,and fuels for use in internal combustion engines and the machinery ofmotorized vehicles.

2. State of the Art

Monomeric norbornyl ester adducts of O,O-dialkyldithiophosphoric acidhave been disclosed in the art. For example, in U.S. Pat. No. 3,023,209,various dialkyl-dithiophosphoric acid esters of norbornene reactants aredisclosed as possessing good insecticidal, fungicidal and miticidalproperties. It is also disclosed that these compounds have propertiesrendering them useful as corrosion inhibitors, plasticizing agents,lubricating oil additives and flotation agents, etc.

U.S. Pat. No. 3,962,105 discloses various diesters and/or ester lactonesof norbornene systems which are useful as seal swell additives.

In U.S. Pat. No. 4,028,258, a transmission fluid is disclosed comprisingan alkylene oxide adduct of a phosphosulfurized N-(hydroxyalkyl) alkenylsuccinimide.

Insecticidal alkoxy and haloalkoxyphenol-phosphinyloxy andphosphinothioloxy-1,3-isoindoledones are disclosed in U.S. Pat. No.3,401,175.

In U.S. Pat. No. 2,644,002, dialkyldithio-phosphoric acid esters ofsuccinimides are disclosed as being adaptable for various uses such asinsecticides, fungicides, plasticizers, corrosion inhibitors, flotationagents, and petroleum additives.

Diesters of 1,3-bis(carboxymethyl) adamantanes which are useful asoiling agents for synthetic fibers and as synthetic lubricating oilbases are disclosed in U.S. Pat. No. 3,849,473.

None of the foregoing disclosures teach the norbornyldialkyldithiophosphoric acid adduct, dimer ester or polyester productsof the present invention. Futhermore, there is no disclosure of suchproducts utilized as extreme pressure agents, and antiwear agents orfriction modifying agents for functional fluids to be used in internalcombustion engines and the machinery of a motorized vehicle.

SUMMARY OF THE INVENTION

In accordance with the present invention novel dimer ester and polyestermaterials derived from adducts of O,O-dialkyldithiphosphoric acids and5-norbornene-2,3-dicarboxylic anhydride have been discovered.

Further, in accordance with the present invention functional fluids,e.g., lubricants and fuels comprising a friction modifying, extremepressure and/or antiwear effective amount of the dimer or polymerproducts of the present invention are provided.

Still further in accordance with the invention, additives andconcentrates comprising a diluent/solvent and one or more of thenorbornyl containing reaction products of the present invention areprovided for formulating with functional fluids.

Still further in accordance with the present invention, a method forimproving the load bearing characteristics and fuel economy propertiesof functional fluids used in motorized vehicles is provided.

These and other aspects of the invention will become clear to thoseskilled in the art upon the reading and understanding of thespecification.

DETAILED DESCRIPTION OF THE INVENTION

The norbornyl dimer ester adducts of the present invention may berepresented by the following formula I:

    A--T--A                                                    (I)

wherein A is ##STR1## where R is alkyl, aryl or aralkyl and R¹ is,independently, hydrogen or hydrocarbyl and T is hydrocarbyl.

The norbornyl polyester adduct according to the present invention may berepresented by the formula II:

    Y--D].sub.p [E].sub.r X                                    II

wherein X and Y are terminal groups of the polymer and are,independently, hydrogen, alkyl, aryl, aralkyl, hydroxy, alkoxy,carboalkoxy, aryloxy, dialkylamino, diarylamino, alkylthio or arylthio;p is 3 to about 30; r is 0 to about 30 and the sum of p+r ranges from 3to about 40; D is ##STR2## wherein R is alkyl, aryl or aralkyl and R²and R³ are a bond to other repeating units; and E is ##STR3## wherein R⁴and R⁵ are the same or different and are hydrocarbyl which includesbranched hydrocarbyl groups containing reactive functionalities thereof,and n is 0 or 1.

For the purposes of the present invention, formula (II) is intended torandom and alternating polymers, as well as block and graft copolymers.In the event formula (II) represents a block copolymer, the respectivehomogeneous blocks of repeating D and E segments may each compriserandom or alternating sequences within each of these segments.

As used herein, the terms "hydrocarbyl" or "hydrocarbon-based" denote aradical having a carbon atom directly attached to the remainder of themolecule and having predominantly hydrocarbon character within thecontext of this invention. Such radicals include the following:

(1) Hydrocarbon radicals; that is, aliphatic, (e.g., alkyl or alkenyl),alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- andalicyclic-substituted aromatic, aromatic-substituted aliphatic andalicyclic radicals, and the like, as well as cyclic radicals wherein thering is completed through another portion of the molecule (that is, anytwo indicated substituents may together form an alicyclic radical). Suchradicals are known to those skilled in the art; examples include methyl,ethyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl,eicosyl, cyclohexyl, phenyl and naphthyl (all isomers being included).

(2) substituted hydrocarbon radicals; that is, radicals containingnon-hydrocarbon substituents which, in the context of this invention, donot alter the predominantly hydrocarbon character of the radical. Thoseskilled in the art will be aware of suitable substituents (e.g, halo,hydroxy, alkoxy, carbalkoxy, nitro, alkylsulfoxy).

(3) Hetero radicals; that is, radicals which, while predominantlyhydrocarbon in character within the context of this invention, containatoms other than carbon atoms. Suitable hetero atoms will be apparent tothose skilled in the art and include, for example, nitrogen, oxygen,phosphorus and sulfur.

Terms such as "alkyl-based radical", "aryl-based radical" and the likehave meaning analogous to the above with respect to alkyl and arylradicals and the like.

The radicals are usually hydrocarbon and especially lower hydrocarbon,the word "lower" denoting radicals containing up to seven carbon atoms.They are preferably lower alkyl or aryl radicals, most often alkyl.

The preparation of the norbornene starting material used to react withthe dialkyldithiophosphoric acid, i.e., 5-norbornene-2,3-dicarboxylicanhydride is described in Onishchenko, Diene Synthesis (translation fromthe Russian by Isreal Program for Scientific Translations, Jerusalem,1964), Daniel Davey and Company, Publisher, New York (1964), pages 38,47, 48-50. In general, the preparation of this reaction product involvesthe reaction of dicyclopentadiene with maleic anhydride to produce thedesired 5-norbornene-2,3-dicarboxylic anhydride.

The above norbornene dicarboxylic anhydride reactant is then reactedwith a dialkyldithiophosphoric acid of the formula:

    (RO).sub.2 P(S)SH

to form the norbornyl dialkydithiophosphate intermediate anhydride. Thismaterial may be represented by the following formula: ##STR4## Thealkyl, aryl or aralkyl group R of the phosphoric acid may contain 1 toabout 30 carbon atoms and preferably 3 to about 12 carbon atoms. The Rgroup may be the same or different dependent upon the properties desiredto impart to the particular functional fluid, e.g., oil solubility,antiwear and the like. Also, the anhydride group on the norbornyl ringmay be in the endo or exo position or there may be mixtures of theseisomers.

The above compound (represented by formula III) is further reacted withother reagents in order to produce the dimer ester (I) or polyester (II)products.

The dimer esters of (I) may be prepared by condensing the anhydrideadduct (III) with diols (or polyols), or with mixtures of diols (orpolyols) and monoalcohols, in ratios such that the products are dimeric.For example, with a glycol, HO--R² --OH, (III) gives ##STR5## wherein R¹is H or hydrocarbyl, i.e., a primary or secondary C₂ to C₂₀₀ alkyl,aralkyl, aryl or alkylaryl (linear or branched), and may containunsaturation, halogen or heteroatoms, alicyclic or heterocyclic rings,fused rings. It may also have pendant or incorporated functionality suchas --OH, --NR₂, carbonyl in a diversity of structures (ester, carboxylicacid, aldehyde, ketone, amide or imide), corresponding thio-carbonylmoieties (thioesters, thiolesters, dithioesters, thio- anddithiocarbamates), halogen, alkoxy, alkylthio, mercapto, phosphate,phosphite, phosphonate, dithiophosphate and/or phosphoramide moietiesand wherein R² is C₂ to C₂₀₀ alkylene or arylene (linear or cyclic instructure), having optionally one or more heteroatoms such as halogen,O, S, or N which can also contain one or more polar functions includingthose described for R¹ above.

Furthermore, R² may be polymeric in nature, derived from ring-openingreactions of epoxides, lactones or lactams, or through condensationreactions of diols or aminoalcohol with lactones, lactams, epoxides,and/or dicarboxylic acids (or their esters).

Other useful polymeric R² radicals may be derived from other suchhydroxy-containing polymers as sugars, starches, alkyl alcoholcopolymers, polyvinyl alcohol and partially-hydrolyzed polyvinylcarboxylates.

When R¹ is H, dimer IV may be converted to salts of metals selected fromGroup IA and IIA of the periodic table, as well as from the varioustransition metals which include Zn, Cd, Sn, Pb, Sb, Cu, Ni, Mn, Co, Fe,Ce, Ti, Zr, the lanthanides, and the complex uranyl cation, UO₂ ⁺².

The salts of adduct (IV) may be made more soluble in oil or in aqueoussolution by using appropriate alkyl (R) groups, and by aminecomplexation, where this is feasible (as with transition metal ions).

The polymeric derivatives of adduct (III) may be prepared by thecondensation of diols (and/or polyols) with adduct (III) to produce thepolymeric derivative represented by (II). The condensation reaction iscarried out such that equivalent ratios of OH:C═O (or more usually, withreatios having 1 to 10% excess OH) are used, and the reaction is carriedout to the point of complete removal of water. The products are ofmolecular weights of about 1000 to about 10,000 (usually 1000 to 3000),and are oil-soluble due to the size and nature of the R group in thedithiophosphate ester portion of the molecule.

The polymeric derivatives (II) may be more specifically illustrated bythe following formula: ##STR6## where Q is H, C₁ to C₃₀ alkyl or aryl(or OH-containing alkyl or aralkyl), which also may contain heteroatoms(e.g., O, S, N, P, halogen or other functionality); Z is --OH, C₁ to C₃₀alkoxy, carbalkoxy or aryloxy, which groups may also contain heteroatoms(S, O, N), dialkyl (or diaryl)-amino, or alkylthio, or arylthio, halogenas well as other functionalities; m is 3 to 30; preferably 4 to 10, andR² is the same as described for IV above.

Moreover, di- and/or polycarboxylic acids may be co-condensed withcompound (III) and reactive diols (or polyols). Of particular interestare those acids which are used in the production of other linear orbranched (e.g., alkyd) resins, among which are:

(a) alkyl and alkenyl succinic acids (or the corresponding anhydrides);

(b) C₄ to C₂₀ alpha-omega-dicarboxylic acids (e.g., succinic, glutaric,adipic, azaleic);

(c) the so-called "dimer acids," made by Emery Corp. from vegetableacids, and containing approximately 36 carbon atoms;

(d) the isomeric phthalic acids (in particular iso-phthalic andterephthalic);

(e) maleic, itaconic, citraconic, tricarballylic;

(f) pyromellitic, trimellitic;

(g) tartaric, citric, lactic;

(h) maleinated C₁₁ to C₁₈ fatty acids;

(i) Diels-Alder adducts of 1,3-dienes, such as 1,3-butadiene,cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene,1,3-cyclododecandiene or isoprene with alpha,beta-unsaturateddicarboxylic acids; and

(j) heteroatom-coupled carboxylic acids, such as thiodiacetic,thiopropionic, iminodiacetic, nitroacetic and the like.

The resulting co-condensation products are mixed linear and/or branchedpolyesters of general structure (VI), which exhibit remarkableload-bearing (EP) and antiwear properties in lubricating oilcompositions as well as friction modifying and dispersancy properties.

These polyester products may be represented more specifically by thefollowing formula VI which is encompassed by (II). ##STR7## wherein Qand Z are the same as defined in (V) above; where the sum of n and i ispreferably 3 to 30 and most preferably 4 to 10. R² is the same asdefined in (IV) above and R⁴ is C₂ to C₂₀ alkylene, aralkylene orcycloalkylene, C₆ to C₃₀ arylene or akylarylene [with or withoutheteroatoms, halogen, or other functionality (e.g., carboxylic acid,ester, amide or imide, ketone, aldehyde), hydroxy, alkoxy, alkylthio,carbalkoxy, etc.]

In a preferred embodiment of this invention, R⁴ is derived from a C₁₀ toC₁₀₀ alkenylsuccinic anhydride prepared from a C₈ to C₉₈ olefin orpolyolefin and maleic anhydride at 200°-230° C. in an Alder (or "Ene")condensation. In this instance, oil-solubility and performanceproperties of structure (VI) is dependent on the nature of R in thedithiophosphate portion of the adduct and the pendant hydrocarbon tailof the alkenylsuccinic acid portion of the polyester.

With respect to different polyol and mono- or polycarboxylic acidreactants that may condensed with adduct (III), the selection of thespecific polyol or mono- and/or polyacid is dependent upon theproperties desired for the end product as well as such pragmaticconsiderations as cost. Representative of diols useful in the practiceof this invention are typically dihydric alcohols or functionalderivatives thereof, such as esters, which are capable of condensingwith diacids or their functional derivatives to form condensationpolymers. These diols can be represented, for example, by the formula R⁶O--R² --OR⁶ wherein each R⁶ is hydrogen or alkylcarbonyl, preferably offrom 2 to 7 carbon atoms. An alkylcarbonyl can be represented by theformula ##STR8## wherein R⁷ is alkyl preferably of from 1 to 6 carbonatoms. Representative alkylcarbonyl radicals are acetyl, propionyl,butyryl, etc. More preferably, each R⁶ is hydrogen.

R² is an aliphatic, alicyclic or aromatic radical, preferably of 2 to 12carbon atoms, more preferably of 2 to 6 carbon atoms and, optionally,including, oxygen and/or sulfur atoms. Typical aliphatic, alicyclic andaromatic radicals include alkylene, cycloalkylene, alkylidene, arylene,alkylidyne, alkylenearylene, alkylenecycloalkylene, alkylenebisarylene,cycloalkylenebisalkylene, arylenebisalkylene, alkylene-oxy-alkylene,alkylene-oxy-arylene-oxyalkylene, etc. Preferably, R² is hydrocarbon,such as alkylene, cycloalkylene, cycloalkylenebisalkylene or arylene butmay also contain heteroatoms such as S, N, O, and/or P.

Exemplary diols and polyols that may be mentioned include the aliphaticpolyoxyalkylene glycols, polyethylene glycol, polypropylene gylcol,polyethylene and polypropylene glycol mixtures, diethylene glycol,thiethylene glycol, tetraethylene glycol, pentaethylene glycol,hexaethylene glycol, heptaethylene glycol, oxyethylene glycol,dipropylene glycol, and mixtures thereof. Preferably the polyoxyalkyleneglycol is selected from the group consisting of diethylene glycol,triethylene glycol, and mixtures thereof. Also included arethiodiethanol, dithiodiethanol, di(2-hydroxyethyl)amides and the like.

Other diols useful in the preparation of polymers of the invention alsoinclude non-oxyalkylated aliphatic, cycloaliphatic and aromatic glycols.Representative examples include propylene glycol, 1,3-propane diol,neopentyl glycol, 1,3-butane diol, 1,5-pentane diol, 1,6-hexane diol,catechol, resorcinol, and hydroquinone. Preferred diols of this classare selected from the group consisting of ethylene glycol, propyleneglycol and 1,4-butane diol.

The representative carboxylic acids useful for the present inventioninclude any suitable polycarboxylic acid such as oxalic acid, malonicacid, succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, maleic acid, fumaric acid, glutaconicacid, alpha-hydromuconic acid, beta-hydromuconic acid,alpha-butyl-alpha-ethyl-glutaric acid, alpha,beta-diethylsuccinic acidand 1,4-cyclohexane-dicarboxylic acid, 4-cyclohexane-1,2-dicarboxylicacid, 2-ethylsuberic acid, 2,2,3,3-tetramethylsuccinic acid,4,4'-bicyclohexyldicarboxylic acid, diglycolic, thiodipropionic, andother similar acids including those disclosed, for example, in U.S. Pat.Nos. 3,546,180; 3,929,489; and 4,101,326. Alkyl ester, acid halide andanhydride derivatives of these acids are also useful in the practice ofthis invention.

Representative unsaturated dicarboxylic acid reactants include aromaticacids including phthalic, terephthalic, isophthalic, 2,5-norbornanedicarboxylic, 1,4-naphthalic, diphenic, 4,4-oxydibenzoic,4,4'-sulfonyldibenzoic, and 2,5-naphthalene dicarboxylic acids.

Representative polyfunctional reactants are trimesic acid, trimelliticacid, trimellitic anhydride, pyromollitic acid, butanetetracarboxylicacid, naphthalenetricarboxylic acids, cyclohexane-1,3,5-tricarboxylicacid, glycerol, trimethylolpropane, pentaerythritol, dipentaerthritol,1,2,6-hexanetroil, 1,3,5-trimethylolbenzene, malic acid, citric acid,3-hydroxyglutaric acid, 4-beta-hydroxyethylphthalic acid,2,2-dihydroxymethylpropionic acid, 10,11-dihydroxyundecanoic acid,5-(2-hydroxyethoxy)isophthalic acid and others known in the art asdisclosed, for example, in U.S. Pat. No. 4,013,624.

The dimer esters and polyesters of this invention can be prepared bystandard procedures. Typically, such procedures involve the reaction ofthe dicarboxylic acids (or diesters, anhydrides, etc., thereof) withpolyhydric alcohols in the presence of an acid catalyst, such as an arylsulfonic acid or alkyl sulfonic acid, or an organic titanate, such astetrabutyl titanate, utilizing heat and reduced pressure as desired.Normally, an excess of the volatile polyhydric alcohol is supplied andremoved by conventional techniques in the latter stages ofpolymerization. To protect the polyester from oxidation, an antioxidantsuch as a hindered phenol can be added to the reaction mixture.

In general, the dimer ester and polyester products of the presentinvention may be described as the reaction product of

(A) 5-norbornene-2,3-dicarboxylic anhydrides;

(B) O,O-dialkyldithiophosphoric acid; and

(C) at least one diol and/or polyol and, optionally, at least one mono-,di- or polycarboxylic acid.

The preparation of various dimer ester and polyester species within thescope of the present invention is illustrated in the following examples.While these examples will show one skilled in the art how to operatewithin the scope of this invention, they are not to serve as alimitation on the scope of the invention where such scope is definedonly in the claims. It is pointed out that in the following examples,all percentages and all parts are intended to express percent by weightand parts by weight unless otherwise clearly indicated.

EXAMPLE 1 Preparation of Adduct of Di-isooctyl dithiophosphoric Acid and5-Norbornene-2,3-dicarboxylic Anhydride

A reaction flask was charged with 911 grams of5-norbornene-2,3-dicarboxylic anhydride and 750 ml of toluene, heated to70° C. to effect dissolution. After purging the system with inertnitrogen gas, 1980 grams of O,O-di-isooctyl dithiophosphoric acid wasadded in a continuous manner at 80°-90° C. over a period of 2 hours. Thehomogeneous solution was held at 90° C. for an additional 5 hours withstirring under a low nitrogen sparge, during which time the strong acidnumber (bromphenol blue indicator) of the reaction mixture decreasedrapidly.

The solution was then vacuum-stripped at 90°-100° C. 5 torr, andfiltered through a thin pad of diatomaceous earth to give 2723 grams(94% yield) of clear amber adduct (Structure III; R=isooctyl) having abromphenol blue acid number of 2.6. The infrared specturm of the liquidshowed absorptions at 1775 and 1850 cm-¹, indicative of 5-memberedcyclic anhydride. Analysis: %S=11.4; %N=5.96.

EXAMPLE 2 Polyester from Ethylene Glycol

A reaction flask was charged with 560 grams of the anhydride product ofExample 1, 75 grams of ethylene glycol, 300 grams of toluene and 2 gramsof p-toluenesulfonic acid, and heated to reflux under a gentle sparge ofnitrogen. Water of condensation was removed ocer a 10-hour period byazeotropic distillation, then the solution was cooled and washed twicewith 500-ml portions of water, and stripped to 120° C./10 torr.Filtration through diatomaceous earth gave a viscous amber oil, apolyester containing 10.5% sulfur, and having an acid number(phenolpthalein indicator) of 28.

EXAMPLE 3 Polyester from Ethylene Glycol and C₁₈ -C₂₄ AlkenylsuccinicAnhydride

The reaction container was charged with 560 g of the product of Example1, 136 g of ethylene glycol and 414 g of a C₁₈ -C₂₄ alkenylated succinicanhydride. This mixture was stirred and 1.9 g of p-toluenesulfonic acidcatalyst was added to the mixture. The reaction mixture was furtherheated. At 110° C., 500 ml foluene was added to the reaction. Thetemperature was kept high enough to maintain a reflux. Water was removedby azeotropic distillation. After approximately 5 hrs., 16 ml water hadbeen removed and the reaction was cooled overnight. The reaction wasreheated to reflux for 6 hrs. The reaction mixture was stripped at 120°C./10 mm Hg. The product was then filtered through a cloth pad anddiatomaceous earth filter aid.

EXAMPLE 4 Polyester/Urethane from Ethylene Glycol andToluenediisocyanate

A reaction flask was charged with 489 grams of the product of Example 1,400 ml of toluene, 160 grams of ethylene glycol and 1.5 gram ofp-toluenesulfonic acid. The reaction mixture was stirred and heated togentle reflux under a slow nitrogen sparge, and water of condensation(17 ml; 100% of theory for formation of diester) was removed over aperiod of 8 hr. The reaction mixture was cooled to room temperature,washed with two 500-ml portions of water, then stripped to 110° C./15torr. Filtration through diatomaceous earth gave 590 grams ofbis-(2-hydroxyethyl) ester of the product of Example 1, as a clearyellow, viscous oil containing 10.00%S and having an acid number(phenolphthalein indicator) of 10.

A mixture of 340 grams of this bis-(2-hydroxyethyl) ester and 400 ml ofoil contained in a resin flask is stirred rapidly while 87 grams oftoluenediisocyante is added rapidly. After the addition of 3 grams oftributylamine, the mixture is heated to 100° C. for 2 hr, during whichtime 300 ml of oil is added to ensure a manageable product viscosity.The mixture is then heated to 125° C., and held at that temperature for3 hr. Condensation is followed by monotiring the infrared absorption of--NCO at 2240 cm⁻¹.

Filtration through a cloth pad gives a viscous oil solution ofpolyester/urethane product.

EXAMPLE 5 Polyester Derived from Ethylene Glycol and C₁₅ -C₁₈Alkenylsuccinic Anhydride

A reaction flask was charged with 124 grams of C₁₅ -C₁₈ alkenylsuccinicanhydride, 228 grams of the product of Example 1, 54 grams of ethyleneglycol, 1.5 grams of p-toluenesulfonic acid and 400 ml of toluene. Themixture was heated to reflux with stirring under a gentle nitrogensparge, and maintained at that temperature for 22 hr. to assure completeremoval of water be azeotropic distillation. After cooling, the solutionwas washed with two 500-ml portions of water, and stripped to 110°C./torr. Filtration through diatomaceous earth gave 289 grams of viscousamber oil, containing 6.79% sulfur.

EXAMPLE 6 bis-Half Acid Ester from Pentaerythritol

A reaction mixture consisting of 1140 grams of the anhydride product ofExample 1, 136 grams of monopenterythritol and 300 ml of toleune wasstirred rapidly under nitrogen at 100 C. for one hour. The temperaturewas slowly increased go 120 C. for two hours. The solution was strippedto 120 C./20 torr, then filtered through diatomaceous earth to give 1006grams of visous yellow oil, containing 10.3% sulfur, and having an acidnumber (phenolphthalein indicator) of 90. The product demonstratedecellent solubility in oil at both 1% and 10% concentration.

The dimer and polymer materials of the present invention have been foundto be useful extreme pressure agents and have been found to be usefulextreme pressure agents and antiwear agents as well asfriction-modifying agents.

The materials of the invention may be formulated into a functional fluide.g., crankcase oil, automatic transmission fluid, hydraulic fluid, andthe like by blending with the particular oil or functional fluid to beformulated.

The lubricating oil or other functional fluid may also be formulatedwith compounds of the present invention in the form of a concentrate.Such a concentrate may be prepared by adding 1% to about 99% by weightof at least 1 dimer or polymer of the present invention to asubstantially inert, normally liquid organic diluent or solvent such asbenzene, toluene, xylene, petroleum naphtha, mineral oil,ethylene-glycol-mono-alkylether or the like.

The amount of these additives fromulated with a particular lubricant mayvary over a wide range and must be an amount to effectively impartextreme pressure antiwear, and friction modifying properties in thelubricatn. As a preferred amount, the additive may range from 0.01weight percent to about 10 weight percent of the formulated lubricant.

The dimer and polymer materials of the present invention formulated withthe particular functional fluid may contain other additives andchemistries such as dispersants, antioxidants, and the like. Such otheradditives and chemistries include, for example, detergents anddispersants of the ash-producing or ashless type, corrosion- andoxidation-inhibiting agents, pour point-depressing agents, auxiliaryextreme pressure agents, color stabilizers and anti-foam agents. Theseother additives and chemistries are fully described and disclosed inU.S. Pat. No. 3,541,012; U.S. Pat. No. 3,697,428; and U.S. Pat. No.4,234,435. The disclosures of these patents relating to such otheradditives and chemistries are hereby incorporated by reference for suchdisclosures.

A preferred dispersant according to the present invention is at leastone substituted succinic acid or derivative thereof consisting ofsubstituent groups wherein the substituent groups are derived frompolyalkylene, said polyalkylene being characterized by a Mn value of 500to about 10,000 and a Mw/Mn value of 1.0 to about 4.0.

It has also been found that the additive compounds of the presentinvention are useful in formulating various grease compositions. Thenorbornene dimer and polymer additives of the present invention areuseful in both mineral and synthetic lubricating oils and greases.Synthetic oils include polyolefin oils (e.g., polybutene oil, deceneoilgomer, and the like) synthetic esters (e.g., dinonyl sebacate,trioctanoic acid ester of trimethyolpropane, and the like), polyglycoloils, and the like. Greases are made from these oils by adding athickening agent such as sodium, calcium, lithium, or aluminum salts offatty acids such as stearic acid. These and similar thickening agentsare described in U.S. Pat. Nos. 2,197,263; 2,564,561 and 2,999,066. Theoils and greases of the present invention are prepared by blending anamount of the norbornene dimer or polymer additive of the presentinvention sufficient to impart extreme pressure properties, antiwearproperties and/or friction modifying properties into the oil or grease.A useful concentration may range from about 0.1 to about 5 weightpercent.

To further illustrate various functional fluid compositions,specifically lubricant compositions, comprising the compositions of thepresent invention, the following illustrative examples are provided. Itis again pointed out that the following examples are provided forillustrative purposes only and are not to place any limitation on thescope of the invention where such scope is set out only in the claims.All parts and percentages are by weight.

Typical compositions according to this invention are listed in thefollowing table.

                  TABLE I                                                         ______________________________________                                        COMPONENTS     A      B      C    D    E    F                                 ______________________________________                                        Base Oil       90.37  90.87  92.82                                                                              95.0 81.13                                                                              83.18                             Product of                                  2.00                              Example 2                                                                     Product of     0.11   0.11   3.86 2.50                                        Example 3                                                                     Product of                             2.60                                   Example 4                                                                     Reaction Product                       3.61 2.50                              of Polybutenyl                                                                Succinic Anhydride                                                            with Ethylene                                                                 Polyamine                                                                     Reaction Product                            2.50                              of Polybutenyl                                                                Succinic Anhydride                                                            with Ethylene                                                                 Polyamine and                                                                 Pentaerythritol                                                               Reaction Product                                                                             2.00   2.00                                                    of Polybutenyl                                                                Succinic Anhydride                                                            with Ethylene                                                                 Polyamine and                                                                 Carbon Disulfide                                                              Reaction Product                                                                             1.00   1.00                                                    of Polybutenyl                                                                Succinic Anhydride                                                            with Ethylene                                                                 Polyamine and                                                                 Boric Acid                                                                    Basic Calcium  1.79   1.79                  1.10                              Alkylbenzene-                                                                 sulfonate                                                                     Basic Magnesium                        1.35 0.65                              Alkylbenzene-                                                                 sulfonate                                                                     Reaction Product of                                                                          3.50   3.50   1.11      0.20                                   Maleic Anhydride-                                                             styrene Copolymer                                                             with Alcohol and                                                              Amine                                                                         Hydrogenated Styrene-                  9.00                                   diene Block Copolymer                                                         Viscosity Improver                                                            Ethylene-propylene                          7.00                              Copolymer Viscosity                                                           Improver                                                                      Sulfurized Fat 0.50                                                           Reaction Product of                                                                          0.50   0.50                                                    an Organo Sulfur Cmpd.                                                        with an Epoxide                                                               Sulfurized Olefin                 2.50 1.50                                   Ester of Dimercapto-         0.17      0.10 0.06                              thiadiazole                                                                   Sulfurized Diels-                           0.60                              Alder Adduct                                                                  Oil Soluble                  1.47                                             Phosphorus-Containing                                                         Extreme Pressure Agent                                                        Alkylated Arylamine                                                                          0.10   0.10             0.50 0.30                              Ethoxylated Fatty                                                                            0.09   0.09                                                    Amine                                                                         Fatty Amide                  0.11           0.10                              Fatty Amine                  0.39                                             Silicone Anti- 0.042  0.042  0.066     0.006                                                                              0.006                             foam Agent                                                                    ______________________________________                                    

The products of the various examples, contained in a fully formulatedlubricating composition as is described in Table I, were then testedwith regard to a Timken "OK" load test as well as a contact pressuretest in accordance with ASTM D 2782 with the exception that in the "OK"load test the following procedural differences were made:

1. Test cup and block surfaces are merely "wetted" with test lubricant(approximately 5 drops on block). No test sample is recirculated overthe surfaces during the test.

2. Test duration is 5 minutes under load.

3. This procedure is run as an "OK" Load test, determining "OK" Load asin ASTM Test D 2782 except utilizing the following load increments:

a. "OK" Load is less than or equal to 20 lbs.: Determine "OK" Load tothe nearest 1 lb.

b. "OK" Load is greater than 20 lbs.: Determine "OK" Load using standardload increments as described in ASTM Test D 2782.

The results from testing products of the present invention according tothe above tesr procedure are set out in Table II below.

                  TABLE II                                                        ______________________________________                                        Timken Results                                                                                     #        Unit Press.                                                                           Wt %.sup.1                              No.  Sample          Loading  psi.    P                                       ______________________________________                                        1.   Product of      15       11,725  0.05                                         Example 2                                                                2.   Zinc, 0,0-diis-                  0.05                                         ooctyl dithio-                                                                phosphate                                                                3.   Product of      20       11,950  0.05                                         Structure V,                                                                  where R = isooctyl                                                            isobutyl amyl mixed                                                           alkyl, and R.sup.2 = C.sub.2 H.sub.4-                                    4.   Product of      20       12,700  0.05                                         Example 3                                                                5.   Product of      20       11,200  0.05                                         Example 5                                                                ______________________________________                                         .sup.1 Based on the weight of the phosphorous content on the sample.     

The invention also includes aqueous compositions characterized by anaqueous phase with at least one amine and/or metal salt of at least onedimer or polymer of the present invention dispersed or dissolved in saidaqueous phase. Preferably, this aqueous phase is a continuous aqueousphase although, in some embodiments, the aqueous phase can be adiscontinuous phase. These aqueous compositions usually contain at leastabout 25% by weight water. Such aqueous compositions encompass bothconcentrates containing about 25% to about 80% by weight, preferablyfrom about 40% to about 65% water; and water-based functional fluidscontaining generally over about 80% by weight of water. The concentratesgenerally contain from about 10% to about 90% by weight of at least oneof the dimer or polymer additives of the invention. The water-basedfunctional fluids generally contain from about 0.05% to about 15% byweight of the dimer or polymer materials of the invention. Theconcentrates generally contain less than about 50%, preferably less thanabout 25%, more preferably less than about 15%, and still morepreferably less than about 6% hydrocarbon oil. The water-basedfunctional fluids generally contain less than about 15%, preferably lessthan about 5%, and more preferably less than about 2% hydrocarbon oil.

These concentrates and water-based functional fluids can optionallyinclude other conventional additives commonly employed in water-basedfunctional fluids. These other additives include surfactants;thickeners; oil-soluble, water-insoluble functional additives such asantiwear agents, extreme pressure agents, dispersants, etc.; andsupplemental additives such as corrosion-inhibitors, shear stabilizingagents, bactericides, dyes, water-softeners, odor masking agents,anti-foam agents and the like.

The concentrates are analogous to the water-based functional fluidsexcept except that they contain less water and proportionately more ofthe other ingredients. The concentrates can be converted to water-basedfunctional fluids by dilution with water. This dilution is usually doneby standard mixing techniques. This is often a convenient proceduresince the concentrate can be shipped to the point of use beforeadditional water is added. Thus, the cost of shipping a substantialamount of the water in the final water-based functional fluid is saved.Only the water necessary to formulate the concentrate (which isdetermined primarily be ease of handling and convenience factors), needbe shipped.

Generally these water-based functional fluids are made by diluting theconcentrates with water, wherein the ratio of water to concentrate isusually in the range of about 80:20 to about 99:1 by weight. As can beseen when dilution is carried out within these ranges, the finalwater-based functional fluid contains, at most, an insignificant amountof hydrocarbon oil.

In various preferred embodiments of the invention, the water-basedfunctional fluids are in the form of solutions while in otherembodiments they are in the form of micelle dispersions ormicroemulsions which appear to be true solutions. Whether a solution,micelle dispersion or microemulsion is formed is dependent, inter alia,on the particular components employed.

Also included within this invention are methods for preparing aqueouscompositions, including both concentrates and water-based functionalfluids, containing other conventional additives commonly employed inwater-based functional fluids. These methods comprise the steps of:

(1) mixing at least one dimer or polymer additive of the invention withsuch other conventional additives either simultaneously or sequentiallyto form a dispersion or solution; optionally

(2) combining said dispersion or solution with water to form saidaqueous concentrate; and/or

(3) diluting said dispersion or solution, or concentrate with waterwherein the total amount of water used is in the amount required toprovide the desired concentration of the components of the invention andother functional additives in said concentrates or said water-basedfunctional fluids.

These mixing steps are preferably carried out using conventionalequipment and generally at room or slightly elevated tempertures,usually below 100° C. and often below 50° C. As noted above, theconcentrate can be formed and then shipped to the point of use where itis diluted with water to form the desired water-based functional fluid.In other instances, the finished water-based functional fluid can beformed directly in the same equipment used to form the concentrate orthe dispersion or solution.

The surfactants that are useful in the aqueous compositions of theinvention can be of the cationic, anionic, nonionic or amphoteric type.Many such surfactants of each type are know to the art. See, forexample, McCutcheon's "Emulsifiers & Detergents," 1981, North AmericanEdition, published by McCutcheon Division, MC Publishing Co., Glen Rock,N.J., U.S.A., which is hereby incorporated by reference for itsdisclosures in this regard.

Among the nonionic surfactant types are the alkylene oxide-treatedproducts, such as ethylene oxide-treated phenols, alcohols, esters,amines and amides. Ethylene oxide/propylene oxide block copolymers arealso useful nonionic surfactants. Glycerol esters and sugar esters arealso known to be nonionic surfactants. A typical nonionic surfactantclass useful with the present invention are the alkylene oxide-treatedalkyl phenols such as the ethylene oxide alkyl phenol condensates soldby the Rohm & Haas Company. A specific example of these is Triton X-100which contains an average of 9-10 ethylene oxide units per molecule, hasan HLB value of about 13.5 and a molecular weight of about 628. Manyother suitable nonionic surfactants are known; see, for example, theaforementioned McCutcheon's as well as the treatise "Non-IonicSurfactants" edited by Martin J. Schick, M. Dekker Co., New York, 1967,which is herein incorporated by reference for its disclosures in thisregard.

As noted above, cationic, anionic and amphoteric surfactants can also beused. Generally, these are all hydrophilic surfactants. Anionicsurfactants contain negatively charged polar groups while cationicsurfactants contain positively charged polar groups. Amphotericdispersants contain both types of polar groups in the same molecule. Ageneral survey of useful surfactants is found in Kirk-OthmerEncyclopedia of Chemical Technology, Second Edition, Volume 19, page 507et seq. (1969, John Wiley and Son, New York) and the aforementionedcompilation published under the name of McCutcheon's. These referencesare both hereby incorporated by reference for their disclosures relatingto cationic, amphoteric and anionic surfactants.

Among the useful anionic surfactant types are the widely knowncarboxylate soaps, organo sulfates, sulfonates, sulfocarboxylic acidsand their salts, and phosphates. Useful cationic surfactants includenitrogen compounds such as amine oxides and the well-known quaternaryammonium salts. Amphoteric surfactants include amino acid-type materialsand similar types. Various cationic, anionic and amphoteric dispersantsare available from the industry, particularly from such companies asRohm & Haas and Union Carbide Corporation, both of America. Furtherinformation about anionic and cationic surfactants also can be found inthe texts "Anionic Surfactants," Parts II and III, edited by W. M.Linfield, published by Marcel Dekker, Inc., New York, 1976, and"Cationic Surfactants," edited by E. Jungermann, Marcel Dekker, Inc.,New York, 1976. Both of these references are incorporated by referencefor their disclosures in this regard.

These surfactants, when used, are generally employed in effectiveamounts to aid in the dispersal of the various additivies, particularlythe functional additives discussed below, in the concentrates andwater-based functional fluids of the invention. Preferably, theconcentrates can contain up to about 75% by weight, more preferably fromabout 10% to about 75% by weight of one or more of these surfactants.The water-based functional fluids can contain up to about 15% by weight,more preferably from about 0.05% to about 15% by weight of one or moreof these surfactants.

Often the aqueous compositions of this invention contain at least onethickener for thickening said compositions. Generally, these thickenerscan be polysaccharides, synthetic thickening polymers, or mixtures oftwo or more of these. Among the poly-saccharides that are useful arenatural gums such as those disclosed in "Industrial Gums" by Whistlerand B. Miller, published by Academic Press, 1959. Disclosures in thisbook relating to water-soluble thickening natural gums in herebyincorporated by reference. Specific examples of such gums are gum agar,guar gum, gum arabic, algin, dextrans, xanthan gum and the like. Alsoamong the polysaccharides that are useful as thickeners for the aqueouscompositions of this invention are cellulose ethers and esters,including hydroxy hydrocarbyl cellulose and hydrocarbylhydroxy celluloseand its salts. Specific examples of such thickeners are hydroxyethylcellulose and the sodium salt of carboxymethyl cellulose. Mixtures oftwo or more of any such thickeners are also useful.

It is a general requirement that the thickener used in the aqueouscompositions of the present invention be soluble in both cold (10° C.)and hot (about 90° C.) water. This excludes such materials as methylcellulose which is soluble in cold water but not in hot water. Suchhot-water-insoluble materials, however, can be used to perform otherfunctions such as providing lubricity to the aqueous compositions ofthis invention.

These thickeners can also be synthetic thickening polymers. Many suchpolymers are known to those of skill in the art. Representative of themare polyacrylates, polyacrylamides, hydrolyzed vinyl esters,water-soluble homo- and interpolymers of acrylamidoalkane sulfonatescontaining 50 mole percent at least of acryloamido alkane sulfonate andother comonomers such as acrylonitrile, styrene and the like.Poly-n-vinyl pyrrolidones, homo- and copolymers as well as water-solublesalts of styrene, maleic anhydride and isobutylene maleic anhydridecopolymers can also be used as thickening agents.

Other useful thickeners are known to those of skill in the art and manycan be found in the list in the afore-mentioned McCutcheon Publication:"Functional Materials," 1976, pp. 135-147, inclusive. The disclosurestherein, relative to water-soluble polymeric thickening agents meetingthe general requirements set forth above are hereby incorporated byreference.

Preferred thickeners, particularly when the compositions of theinvention are required to be stable under high shear applications, arethe water-dispersible reaction products formed by reacting at least onehydrocarbyl-substituted succinic acid and/or anhydride represented bythe formula ##STR9## wherein R is a hydrocarbyl group of from about 8 toabout 40 carbon atoms, with at least one water-dispersible amineterminated poly(oxyalkylene) or at least one water-dispersiblehydroxy-terminated polyoxyalkylene. R preferably has from about 8 toabout 30 carbon atoms, more preferably from about 12 to about 24 carbonatoms, still more preferably from about 16 to about 18 carbon atoms. Ina preferred embodiment, R is represented by the formula ##STR10##wherein R' and R" are independently hydrogen or straight chain orsubstantially straight chain hydrocarbyl groups, with the proviso thatthe total number of carbon atoms in R is within the above-indicatedranges. Preferably R' and R" are alkyl or alkenyl groups. In aparticularly advantageous embodiment, R has from about 16 to about 18carbon atoms, R' is hydrogen or an alkyl group of from 1 to about 7carbon atoms or an alkenyl group of from 2 to about 7 carbon atoms, andR" is an alkyl or alkenyl group of from about 5 to about 15 carbonatoms.

The water-dispersible amine terminated poly(oxyalkylene)s are preferablyalpha omega diamino poly(oxyethylene)s, alpha omega diaminopoly(oxypropylene) poly(oxyethylene) poly(oxypropylene)s or alpha omegadiamino propylene oxide capped poly(oxyethylene)s. The amine-terminatedpoly(oxyalkylene) can also be a urea condensate of such alpha omegadiamino poly(oxytheylene)s, alpha omega diamino poly(oxypropylene)poly(oxyethylene) poly(oxypropylene)s or alpha omega diamino propyleneoxide capped poly(oxyethylene)s. The amine-terminated poly(oxyalkylene)can also be a polyamine (e.g., triamino, tetramino, etc.)polyoxyalkylene provided it is amine-terminated and it iswater-dispersible.

Examples of water-dispersible amine-terminated poly(oxyalkylene)s thatare useful in accordance with the present invention are disclosed inU.S. Pat. Nos. 3,021,232; 3,108,011; 4,444,566; and RE 31,522. Thedisclosures of these patents are incorporated herein by reference.Water-dispersible amine terminated poly(oxyalkylene)s that are usefulare commercially available from the Texaco Chemical Company under thetrade name "Jeffamine."

The water-dispersible hydroxy-terminated polyoxyalkylenes areconstituted of block polymers of propylene oxide and ethylene oxide, anda nucleus which is derived from organic compounds containing a pluralityof reactive hydrogen atoms. The block polymers are attached to thenucleus at the sites of the reactive hydrogen atoms. Examples of thesecompounds include the hydroxy-terminated polyoxyalkylenes which arerepresented by the formula ##STR11## wherein a and b are integers suchthat the collective molecular weight of the oxypropylene chains rangefrom about 900 to about 25,000, and the collective weight of theoxyethylene chains constitute from about 20% to about 90%, preferablyfrom about 25% to about 55% by weight of the compound. These compoundsare commercially available from BASF Wyandotte Corporation under thetrade name "Tetronic." Additional examples include thehydroxy-terminated polyoxyalkylenes represented by the formula

    HO(C.sub.2 H.sub.4 O).sub.x (C.sub.3 H.sub.6 O).sub.y (C.sub.2 H.sub.4 O).sub.z H

wherein y is an integer such that the molecular weight of theoxypropylene chain is at least about 900, and x and z are integers suchthat the collective weight of the oxyethylene chains constitute fromabout 20% to about 90% by weight of the compound. These compoundspreferably have a molecular weight in the range of about 1,100 to about14,000. These compounds are commercially available from BASF WyandotteCorporation under the trade name "Pluronic." Useful hydroxy-terminatedpolyoxyalkylenes are disclosed in U.S. Pat. Nos. 2,674,619 and2,979,528, which are incorporated herein by reference.

The reaction between the carboxylic agent and the amine- orhydroxy-terminated polyoxyalkylene can be carried out at a temperatureranging from the highest of the melt temperatures of the reactioncomponents up to the lowest of the decomposition temperatures of thereaction components or products. Generally, the reaction is carried outat a temperature in the range of about 60° C. to about 160° C.,preferably about 120° C. to about 160° C. The ratio of equivalents ofcarboxylic agent to polyoxyalkylene preferably ranges from about 0.1:1to about 8:1, preferably about 1:1 to about 4:1, and advantageouslyabout 2:1. The weight of an equivalent of the carboxylic agent can bedetermined by dividing its molecular weight by the number of carboxylicfunctions present. The weight of an equivalent of the amine-terminatedpolyoxyalkylene can be determined by dividing its molecular weight bythe number of terminal amine groups present. The weight of an equivalentof the amine-terminated polyoxyalkylene can be determined by dividingits molecular weight by the number of terminal amine groups present. Thenumber of terminal amine and hydroxyl groups can usually be determinedfrom the structural formula of the polyoxyalkylene or empiricallythrough well-known procedures. The amine/acids and ester/acids formed bythe reaction of the carboxylic agent and amine-terminated orhydroxy-terminated polyoxyalkylene can be neutralized with, for example,one or more alkali metals, one or more amines, or a mixture thereof, andthus converted to amide/salts or ester/salts, respectively.Additionally, if these amide/acids or ester/acids are added toconcentrates or functional fluids containing alkali metals or amines,amide/salts or ester/salts usually form, in situ.

South African Pat. No. 85/0978 is incorporated herein by reference forits teachings with respect to the use of hydrocarbyl-substitutedsuccinic acid or anhydride/hydroxy-terminated poly(oxyalkylene) reactionproducts as thickeners for aqueous compositions.

When the thickener is formed using an amine-terminatedpoly(oxyalkylene), the thickening characteristics of said thickener canbe enhanced by combining it with at least one surfactant. Any of thesurfactants identified above under the subtitle "Surfactants" can beused in this regard. When such surfactants are used, the weight ratio ofthickener to surfactant is generally in the range of from about 1:5 toabout 5:1, preferably from about 1:1 to about 3:1.

Typically, the thickener is present in a thickening amount in theaqueous compositions of this invention. When used, the thickener ispreferably present at a level of up to about 70% by weight, preferablyfrom about 20% to about 50% by weight of the concentrates of theinvention. The thickener is preferably present at a level in the rangeof from about 1.5% to about 10% by weight, preferably from about 3% toabout 6% by weight of the functional fluids of the invention.

The functional additives that can be used in the aqueous systems aretypically oil-soluble, water-insoluble additives which function inconventional oil-based systems as extreme pressure agents, antiwearagents, load-carrying agents, dispersants, friction modifiers, lubricityagents, etc. They can also function as anti-slip agents, film formersand friction modifiers. As is well known, such additives can function intwo or more of the above-mentioned ways; for example, extreme pressureagents often function as load-carrying agents.

The term "oil-soluble, water-insoluble functional additive" refers to afunctional additive which is not soluble in water above a level of about1 gram per 100 milliliters of water at 25° C., but is soluble in mineraloil to the extent of at least 1 gram per liter at 25° C.

These functional additives can also include certain solid lubricantssuch as graphite, molybdenum disulfide and polytetrafluoroethylene andrelated solid polymers.

These functional additives can also include frictional polymer formers.Briefly, these are potential polymer forming materials which aredispersed in a liquid carrier at low concentration and which polymerizeat rubbing or contacting surfaces to form protective polymeric films onthe surfaces. The polymerizations are believed to result from the heatgenerated by the rubbing and, possibly, from catalytic and/or chemicalaction of the freshly exposed surface. A specific example of suchmaterials is dilinoleic acid and ethylene glycol combinations which canform a polyester frictional polymer film. These materials are known tothe art and descriptions of them are found, for example, in the journal"Wear," Volume 26, pages 369-392, and West German Published PatentApplication 2,339,065. These disclosures are hereby incorporated byreference for their discussions of frictional polymer formers.

Typically these functional additives are known metal or amine salts oforgano sulfur, phosphorus, boron or carboxylic acids which are the sameas or of the same type as used in oil-based fluids. Typically such saltsare of carboxylic acids of 1 to 22 carbon atoms including both aromaticand aliphatic acids; sulfur acids such as alkyl and aromatic sulfonicacids and the like; phosphorus acids such as phosphoric acid, phosphorusacid, phosphinic acid, acid phosphate esters and analogous sulfurhomologs such as the thiophosphoric and dithiophosphoric acid andrelated acid esters; boron acids include boric acid, acid borates andthe like. Useful functional additives also include metaldithiocarbamates such as molybdenum and antimony dithiocarbamates; aswell as dibutyl tin sulfide, tributyl tin oxide, phosphates andphosphites; borate amine salts, chlorinated waxes; trialkyl tin oxide,molybdenum phosphates, and chlorinated waxes.

Many such functional additives are known to the art. For example,descriptions of additives useful in conventional oil-based systems andin the aqueous systems of this invention are found in "Advances inPetroleum Chemistry and Refining," Volume 8, edited by John J. McKetta,Interscience Publishers, New York, 1963, pages 31-38 inclusive;Kirk-Othmer "Encyclopedia of chemical Technology," Volume 12, SecondEdition, Interscience Publishers, New York, 1967, page 575 et seq.;"Lubricant Additives" by M. W. Ranney, Noyes Data Corporation, ParkRidge, N.J., U.S.A., 1973; and "Lubricant Additives" by C. V. Smalheerand R. K. Smith, The Lezius-Hiles Co., Cleveland, Ohio, U.S.A. Thesereferences are hereby incorporated by reference for their disclosures offunctional additives useful in the compositions of this invention.

In certain of the typical aqueous compositions of the invention, thefunctional additive is a sulfur or chlorosulfur extreme pressure agent,known to be useful in oil-base systems. Such materials includechlorinated aliphatic hydrocarbons, such as chlorinated wax; organicsulfides and polysulfides, such as benzyl-disulfide,bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized sperm oil,sulfurized methyl ester of oleic acid, sulfurized alkylphenol,sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alderadducts; phosphosulfurized hydrocarbons, such as the reaction product ofphosphorus sulfide with turpentine or methyl oleate, phosphorus estersuch as the dihydrocarbon and trihydrocarbon phosphites, i.e., dibutylphosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenylphosphite, dipentylphenyl phosphite, tridecyl phosphite, distearylphosphite and polypropylene substituted phenol phosphite; metalthiocarbamates, such as zinc dioctyldithiocarbamate and bariumheptylphenol dithiocarbamate; and Group II metal salts of aphosphorodithioic acid, such as zinc dicyclohexyl phosphorodithioate.

The functional additive can also be a film former such as a synthetic ornatural latex or emulsion thereof in water. Such latexes include naturalrubber latexes and polystyrene butadienes synthetic latex.

The functional additive can also be an anti-chatter or anti-squawkagent. Examples of the former are the amide metal dithiophosphatecombinations such as disclosed in West German Pat. No. 1,109,302; aminesalt-azomethane combinations such as disclosed in British PatentSpecification No. 893,977; or amine dithiophosphate such as disclosed inU.S. Pat. No. 3,002,014. Examples of anti-squawk agents areN-acyl-sarcosines and derivatives thereof such as disclosed in U.S. Pat.Nos. 3,156,652 and 3,156,653; sulfurized fatty acids and esters thereofsuch as disclosed in U.S. Pat. Nos. 2,913,415 and 2,982,734; and estersof dimerized fatty acids such as disclosed in U.S. Pat. No. 3,039,967.The above-cited patents are incorporated herein by reference for theirdisclosure as pertinent to anti-chatter and anti-squawk agents useful asa functional additive in the aqueous systems of the present invention.

Specific examples of functional additives useful in the aqueous systemsof this invention include the following commercially available products.

                  TABLE I                                                         ______________________________________                                        Functional Addi-                                                                            Chemical                                                        tive Trade Name                                                                             Description    Supplier                                         ______________________________________                                        Anglamol 32   Chlorosulfurized                                                                             Lubrizol.sup.1                                                 hydrocarbon                                                     Anglamol 75   Zinc dialkyl   Lubrizol.sup.1                                                 phosphate                                                       Molyvan L     A thiaphos-    Vanderbilt.sup.2                                               phomolybdate                                                    Lubrizol-5315 Sulfurized cyclic                                                                            Lubrizol.sup.1                                                 carboxylate ester                                               Emcol TS 230  Acid phosphate Witco.sup.3                                                    ester                                                           ______________________________________                                         .sup.1 The Lubrizol Corporation, Wickliffe, Ohio, U.S.A.                      .sup.2 R. T. Vanderbilt Company, Inc., New York, New York, U.S.A.             .sup.3 Witco Chemical Corp., Organics Division, Houston, Texas, U.S.A.   

Mixtures of two or more of any of the afore-described functionaladditives can also be used.

Typically, a functionally effective amount of the functional additive ispresent in the aqueous compositions of this invention.

The term "functionality effective amount" refers to a sufficientquantity of an additive to impart desired properties intended by theaddition of said additive. For example, if an additive is arust-inhibitor, a functionally effective amount of said rust-inhibitorwould be an amount sufficient to increase the rust-inhibitingcharacteristics of the composition to which it is added. Similarly, ifthe additive is an antiwear agent, a functionally effective amount ofsaid antiwear agent would be a sufficient quantity of the antiwear agentto improve the antiwear characteristics of the composition to which itis added.

The aqueous systems of this invention often contain at least oneinhibitor for corrosion of metals. These inhibitors can preventcorrosion of either ferrous or non-ferrous metals (e.g., copper, bronze,brass, titanium, aluminum and the like) or both. The inhibitor can beorganic or inorganic in nature. Usually it is sufficiently soluble inwater to provide a satisfactory inhibiting action though it can functionas a corrosion-inhibitor without dissolving in water, it need not bewater-soluble. Many suitable inorganic inhibitors useful in the aqueoussystems of the present invention are known to those skilled in the art.Included are those described in "Protective Coatings for Metals" byBurns and Bradley, Reinhold Publishing Corporation, Second Edition,Chapter 13, pages 596-605. This disclosure relative to inhibitors arehereby incorporated by reference. Specific examples of useful inorganicinhibitors include alkali metal nitrites, sodium di- andtripolyphosphate, potassium and dipotassium phosphate, alkali metalborate and mixtures of the same. Many suitable organic inhibitors areknown to those of skill in the art. Specific examples includehydrocarbyl amine and hydroxy-substituted hydrocarbyl amine neutralizedacid compund, such as neutralized phosphates and hydrocarbyl phosphateesters, neutralized fatty acids (e.g., those having about 8 to about 22carbon atoms), neutralized aromatic carboxylic acids (e.g.,4-tertiarybutyl benzoic acid), neutralized naphthenic acids andneutralized hydrocarbyl sulfonates. Mixed salt esters of alkylatedsuccinimides are also useful. Particularly useful amines include thealkanol amines such as ethanol amine, diethanolamine. Mixtures of two ormore of any of the afore-described corrosion-inhibitors can also beused. The corrosion-inhibitor is usually present in concentrations inwhich they are effective in inhibiting corrosion of metals with whichthe aqueous composition comes in contact.

Certain of the aqueous systems of the present invention (particularlythose that are used in cutting or shaping of metal) can also contain atleast one polyol with inverse solubility in water. Such polyols arethose that become less soluble as the temperature of the waterincreases. They thus can function as surface lubricity agents duringcutting or working operations since, as the liquid is heated as a resultof friction between a metal workpiece and work tool, the polyol ofinverse solubility "plates out" on the surface of the workpiece, thusimproving its lubricity characteristics.

The aqueous systems of the present invention can also include at leastone bactericide. Such bactericides are well known to those of skill inthe art and specific examples can be found in the afore-mentionedMcCutcheon publication "Functional Materials" under the heading"Antimicrobials" on pages 9-20 thereof. This disclosure is herebyincorporated by reference as it relates to suitable bactericides for usein the aqueous compositions or systems of this invention. Generally,these bactericides are water-soluble, at least to the extent to allowthem to function as bactericides.

The aqueous systems of the present invention can also include such othermaterials as dyes, e.g., an acid green dye; water softeners, e.g.,ethylene diamine tetraacetate sodium salt or nitrilo triacetic acid;odor masking agents, e.g., citronella, oil of lemon, and the like; andanti-foamants, such as the well-known silicone anti-foamant agents.

The aqueous systems of this invention may also include an antifreezeadditive where it is desired to use the composition at a lowtemperature. Materials such as ethylene glycol and analogouspolyoxyalkylene polyols can be used as antifreeze agents. Clearly, theamount used will depend on the degree of antifreeze protection desiredand will be known to those of ordinary skill in the art.

It should also be noted that many of the ingredients described above foruse in making the aqueous systems of this invention are industrialproducts which exhibit or confer more than one property on such aqueouscompositions. Thus, a single ingredient can provide several functionsthereby eliminating or reducing the need for some other additionalingredient. Thus, for example, and extreme pressure agent such astributyl tin oxide can also function as a bactericide.

While the invention has been described and illustrated with reference tocertain preferred embodiments thereof, those skilled in the art willappreciate that various changes, modifications and substitutions can bemade therein without departing from the spirit of the invention. Forexample, different concentration ranges other than the preferred rangesset forth hereinabove may be applicable as a consequence of variationsin the oil base stock or the type of engine or the like. It is intended,therefore, that the invetnion be limited only by the scope of the claimswhich follow.

What is claimed is:
 1. A dimer ester of the formula:

    A--T--A                                                    (I)

wherein A is ##STR12## where R is alky, aryl or aralkyl and R¹ is,independently hydrogen or hydrocarbyl and T is hydrocarbyl.
 2. The dimerester according to claim 1 wherein R is alkylene of 1 to about 6 carbonatoms, and R¹ is alkyl of 2 to about 12 carbon atoms.
 3. The dimer esteraccording to claim 2 wherein R is ethylene, and R¹ is alkyl of 2 toabout ∂carbon atoms.
 4. A polyester of the formula:

    Y--D].sub.p [E].sub.r X

wherein X and Y are terminal groups of the polymer and are,independently, hydrogen, alkyl, aryl, aralkyl, hydroxy, alkoxy,carboalkoxy, aryloxy, dialkylamino, diarylamino, alkylthio or arylthio;p is 3 to about 30; r is 0 to about 30 and the sum of p+r ranges from 3to about 40; D is ##STR13## wherein R is alkyl, aryl or aralkyl and R²and R³ are hydrocarbyl or a bond to other repeating units; and E is##STR14## wherein R⁴ and R⁵ are the same or different and arehydrocarbyl which includes branched hydrocarbyl groups containingreactive functionalities thereof, and n is 0 or
 1. 5. The polyesteraccording to claim 4 wherein p is 4 to 10, r is 0, and R³ alkylene of 1to about 6 carbon atoms.
 6. The polyester according to claim 5 whereinR³ is ethylene.
 7. The polyester according to claim 4 wherein p is 4 to10, r is 3 to 10 and the sum of p+r ranges from 7 to 12; R³ is alkyleneof 1 to about 6 carbon atoms; R⁴ and R⁵ are alkylated succinic radicalswherein the alkyl group contains abour 8 to about 200 carbon atoms.
 8. Adiester prepared from reactants comprising:(A)5-norbornene-2,3-dicarboxylic anhydrides; (B)0,0-dialkyldithiophosphoric acid containing 1 to about 30 carbon atoms;and (C) a polyol; wherein the adduct of (A) and (B) is condensed withpolyol (C) in such a ratio and under conditions such that the product isa dimeric ester of the formula: A-T-A wherein A is ##STR15## where R isalkyl, aryl or aralkyl and R¹ is, independently, hydrogen or hydrocarbyland T is hydrocarbyl.
 9. The dimer ester according to claim 8 whereinsaid polyol is an alkylene glycol.
 10. The dimer ester according toclaim 9 wherein said alkylene glycol is ethylene glycol.
 11. A polyesterprepared from reactants comprising:(A) 5-norbornene-2,3-dicarboxylicanhydrides; (B) 0,0-dialkyldithiophosphoric acid containing 1 to about30 carbon atoms; and (C) a polyol; wherein the reaction is carried outsuch that equivalent ratios of OH:C═0 are used, the reaction is carriedout to the point of complete removal of water and the polyester preparedhas a molecular weight of about 1000 to about 10,000.
 12. The polyesteraccording to claim 11 wherein said polyol is an alkylene glycol.
 13. Thepolyester according to claim 12 wherein said alkylene glycol is ethyleneglycol.
 14. The polyester according to claim 11 wherein said polyesteris further prepared from an additional polycarboxylic acid or derivativethereof.
 15. The polyester according to claim 14 wherein said additionalpolycarboxylic acid is an alkylated succinic acid or derivative thereofwherein said alkyl group contains about 8 to about 200 carbon atoms. 16.A lubricating composition comprising a major amount of a lubricating oilof lubricating viscosity and a minor effective amount of at least onedimer ester and/or polyester of any one of claims 1 to
 15. 17. Aconcentrate for formulating a lubricant composition comprising fromabout 1% to about 99% by weight of at least one dimer ester and/orpolyester of any one of claims 1 to 15 and a normally liquid,substantially inert organic solvent/diluent.
 18. An additive forformulating lubricant compositions comprising at least one dimer esteror polyesters of any one of claims 1 to
 15. 19. A method for improvingthe load bearing properties and dispersancy of lubricant compositions byadmixing a minor effective amount of at least one dimer ester and/orpolyester of any one of claims 1 to 15 with a major amount of alubricating oil of lubricating viscosity.
 20. A grease compositioncomprising a minor effective amount of at least one dimer ester orpolyester of any one of claims 1 to
 15. 21. An aqueous functional fluidcomprising a minor effective amount of at least one dimer ester orpolyester of any one of claims 1 to 15.